KR20070086388A - Graft copolymer and solution type water-and-oil repellant composition containing the same - Google Patents

Abstract

A solution type water-and-oil repellant composition comprising: a graft copolymer having repeating units derived from a vinyl monomer having a perfluoroalkyl group and repeating units derived from a polymerizable cyclic acid anhydride; and an organic solvent. The composition has high product stability, is highly stable to dilution, and can impart high water and oil repellency.

Description

Graft copolymer and solution-type water and oil repellent composition using same {GRAFT COPOLYMER AND SOLUTION TYPE WATER-AND-OIL REPELLANT COMPOSITION CONTAINING THE SAME}

The present invention relates to a graft copolymer and a solution-type water / oil repellent composition using the same.

In view of Freon's regulatory and environmental concerns, solvents in water and oil repellent products are being converted from halogen solvents, such as R113, to petroleum solvents. However, there is a problem that the product solidifies or precipitates at low temperatures only by changing the solvent. In particular, precipitation or concentration distribution occurs when the water- and oil-repellent product is diluted using a low-soluble petroleum solvent such as a solvent having a low content of aromatic compounds.

In order to impart high product stability and dilution stability to the water / oil repellent composition, lowering the fluorine concentration in the water / oil repellent active ingredient lowers the water / oil repellent performance.

Japanese Patent Laid-Open No. 61-50082 discloses a water and oil repellent consisting of a graft copolymer obtained by graft polymerization using the reactivity of an OH group. However, since the hydroxyl group remains in the polymer, the graft copolymer has insufficient water repellency. Do.

Japanese Patent Application Laid-Open No. 06-228534 discloses a water / oil repellent agent consisting of a fluorine-based graft copolymer, but since the repeating unit derived from the fluorine-based monomer is included only in the polymer main chain, the fluorine-based graft copolymer is soluble in petroleum solvents. This is insufficient.

Japanese Patent Application Laid-Open No. 09-95516 discloses a water and oil repellent agent containing a perfluoroalkyl vinyl monomer copolymer containing an acid anhydride. However, since the copolymer is not a graft, solubility is insufficient unless the fluorine content is suppressed. Do.

Summary of the Invention

An object of the present invention is to obtain a water / oil repellent having improved solubility in water repellency (particularly, cellulose fibers such as cotton) and petroleum solvents (particularly dearomatic solvents).

By introducing an acid anhydride structure into the graft copolymer, the present inventors have improved the solubility of the petroleum-based solvent of the propellant due to its easily soluble property, and the adhesion to the fiber due to the polarity of the acid anhydride structure (the acid anhydride structure and It has been found that the water- and oil-repellent agent gives both performances of the water-repellency improvement according to the interaction of the cellulose fiber including cotton, in particular with the hydroxyl group).

The present invention provides a solution-type water and oil repellent composition containing a repeating unit derived from a vinyl monomer having a perfluoroalkyl group, a graft copolymer having a repeating unit derived from a polymerizable cyclic acid anhydride, and an organic solvent.

The present invention also provides a graft copolymer having repeating units derived from a vinyl monomer having a perfluoroalkyl group, and repeating units derived from a polymerizable cyclic acid anhydride.

For example, in graft copolymers, the polymer backbone

(A) a vinyl monomer having a perfluoroalkyl group, if necessary,

(B) a non-fluorine vinyl monomer present as needed,

(C) polymerizable cyclic acid anhydrides, if necessary,

(D) a vinyl monomer having a group bonded to the polymer side chain

Consisting of,

Polymer side chains,

(E) a vinyl monomer containing a perfluoroalkyl group present if necessary,

(F) a non-fluorine vinyl monomer present as needed,

(G) polymerizable cyclic acid anhydrides present as necessary

It consists of

At least one of a component (A) and a component (E) is an essential component, and at least one of a component (C) and a component (G) is an essential component.

Examples of the graft copolymers include the following:

(i) a polymer main chain containing a perfluoroalkyl group-containing vinyl monomer (A) and a polymerizable cyclic acid anhydride (C), containing a perfluoroalkyl group-containing vinyl monomer (E) and a polymerizable cyclic acid anhydride (G) Graft copolymers having a polymer side chain;

(ii) a polymer backbone containing a perfluoroalkyl group-containing vinyl monomer (A) and not containing a polymerizable cyclic acid anhydride (C) and a polymerizable cyclic acid anhydride (G) and containing a perfluoroalkyl group-containing vinyl monomer Graft copolymers having a polymer side chain not containing (E);

(iii) a polymer backbone containing a polymerizable cyclic acid anhydride (C) and not containing a perfluoroalkyl group-containing vinyl monomer (A), a polymerizable cyclic acid anhydride containing a perfluoroalkyl group-containing vinyl monomer (E) Graft copolymers having a polymer side chain containing no G);

(iv) a polymer main chain containing a perfluoroalkyl group-containing vinyl monomer (A) and a polymerizable cyclic acid anhydride (C), and a polymerizable cyclic acid anhydride (G) containing a perfluoroalkyl group-containing vinyl monomer (E) Graft copolymers having a polymer side chain not containing;

(v) a polymer backbone containing a polymerizable cyclic acid anhydride (C) and not containing a perfluoroalkyl group-containing vinyl monomer (A), a perfluoroalkyl group-containing vinyl monomer (E) and a polymerizable cyclic acid anhydride (G) Graft copolymer which has a polymer side chain containing these;

(vi) a polymer main chain containing a perfluoroalkyl group-containing vinyl monomer (A) and not containing a polymerizable cyclic acid anhydride (C), a perfluoroalkyl group-containing vinyl monomer (E) and a polymerizable cyclic acid anhydride (G) Graft copolymer which has a polymer side chain containing these;

(vii) a polymer backbone containing a perfluoroalkyl group-containing vinyl monomer (A) and a polymerizable cyclic acid anhydride (C), a polymerizable cyclic acid anhydride (G), and a perfluoroalkyl group-containing vinyl monomer (E) Graft copolymers having a polymer side chain not containing;

(viii) a polymer backbone containing a perfluoroalkyl group-containing vinyl monomer (A) and a polymerizable cyclic acid anhydride (C), a non-fluorine-based vinyl monomer (F), and a polymerizable cyclic acid anhydride (G) and a perfluoro Graft copolymer which has a polymer side chain which does not contain an alkyl group containing vinyl monomer (E);

(ix) Polymer backbone, polymerizable cyclic acid anhydride (G) and perfluor containing non-fluorinated vinyl monomer (B) and not containing perfluoroalkyl group-containing vinyl monomer (A) and polymerizable cyclic acid anhydride (C) Graft copolymer which has a polymer side chain containing a low alkyl group containing vinyl monomer (E).

The perfluoroalkyl group-containing vinyl monomers (A) and (D) forming the polymer main chain and / or the polymer side chain may be (meth) acrylates having a perfluoroalkyl group.

The perfluoroalkyl group-containing (meth) acrylate may be represented by the following general formula.

Rf-A ² -OCOR ¹⁸ = CH ₂

[Wherein Rf is a perfluoroalkyl group having 3 to 21 carbon atoms, R ¹⁸ is hydrogen or a methyl group, and A ² is a divalent organic group.]

As perfluoroalkyl group containing (meth) acrylate, the following can be illustrated, for example.

Rf-O-Ar-CH ₂ OCOCR ³ ≡CH ₂

[Wherein Rf is a perfluoroalkyl group having 3 to 21 carbon atoms, R ¹ is hydrogen or an alkyl group having 1 to 10 carbon atoms, R ² is an alkylene group having 1 to 10 carbon atoms, R ³ is a hydrogen or methyl group, and Ar is a substituent Arylene group which may have, n is an integer of 1-10.

Specific examples of the perfluoroalkyl group-containing (meth) acrylate are as follows.

The said perfluoroalkyl group containing (meth) acrylate can also be used in mixture of 2 or more type.

The vinyl monomer having a perfluoroalkyl group may use another fluorine monomer. In other fluorine-based monomer may be a fluorinated olefin (having a carbon number of, for example 3 to 20) such as _{CF 3 (CF 2) 7 CH} = CH 2 and the like.

Examples of the non-fluorine vinyl monomers (B) and (F) include (meth) acrylate esters. The (meth) acrylate ester may be an ester of (meth) acrylic acid with an aliphatic alcohol such as monohydric alcohol or polyhydric alcohol (such as dihydric alcohol).

Examples of the non-fluorine vinyl monomers include the following.

2-ethylhexyl (meth) acrylate, cyclohexyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, hydroxyalkyl (meth) acrylate, tetrahydrofurfuryl (meth) Acrylate, polyoxyalkylene (meth) acrylate, 3-chloro-2-hydroxypropyl (meth) acrylate, glycidyl (meth) acrylate, N, N-dimethylaminoethyl (meth) acrylate, N, N-diethylaminoethyl (meth) acrylate, benzyl (meth) acrylate glycidyl methacrylate, hydroxypropyl monomethacrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2- Hydroxyethyl acrylate, glycerol monomethacrylate, β-acryloyloxyethylhydrogen succinate, β-methacryloyloxyethylhydrogenphthalate, 2-acryloyloxyethylhexahydrophthalic acid, 2-acrylic Loyloxyethylphthalic acid, 2 -Acryloyloxyethyl-2-hydroxyethylphthalic acid, methacrylic acid hydroxypropyl trimethylammonium chloride, dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate, 2-acryloyloxyethyl acid phosphate, gluco Silethyl methacrylate, methacrylamide, 2-hydroxy-3-acryloyloxypropyl methacrylate, 2-methacryloyloxyethyl acid phosphate, hydroxy pivalate neopentyl glycol diacrylate, etc. (Meth) acrylates; Styrenes such as styrene and p-isopropylstyrene; (Meth) acrylamides, such as (meth) acrylamide, diacetone (meth) acrylamide, N-methylol (meth) acrylamide, N-butoxymethyl acrylamide, and 2-acrylamide-2-methylpropanesulfonic acid ; Vinyl ether, such as vinyl alkyl ether.

In addition, vinyl halides such as ethylene, butadiene, vinyl acetate, chloroprene and vinyl chloride, vinylidene halides, acrylonitrile, vinyl alkyl ketones, N-vinylcarbazole, vinylpyrrolidone, and (meth) acrylic acid may be mentioned. .

In addition, the non-fluorine vinyl monomer may be a silicon-based monomer (for example, (meth) acryloyl group-containing alkylsilane, (meth) acryloyl group-containing alkoxysilane, (meth) acryloyl group-containing polysiloxane).

Examples of the silicon monomers include (meth) acryloxytrialkylsilanes, (meth) acryloxytrialkoxysilanes, (meth) acryloxypolysiloxanes, (meth) acryloxypropyltrialkylsilanes, (meth) acryloxypropyltrialkoxysilanes, (Meth) acryloxypropyl polysiloxane, allyl trialkylsilane, allyltrialkoxysilane, allyl polysiloxane, vinyl trialkylsilane, vinyltrialkoxysilane, and vinyl polysiloxane are mentioned.

(Meth) acryloxypropylpolysiloxane

[Wherein R ²⁰ is H or CH ₃ , R ²¹ is H or CH ₃ , R ²² is H or CH ₃ , R ²³ is H or CH ₃ , n is from 1 to 100]

(Eg, (meth) acryloxypropylpolydimethylsiloxane).

The non-fluorine-based vinyl monomer may be used by mixing two or more kinds.

The polymerizable cyclic acid anhydrides (C) and (G) are carbon-carbon double bonds copolymerizable with vinyl monomers (eg, perfluoro and / or non-fluorinated vinyl monomers) in one molecule, and at least one intramolecular cyclic carboxylic acid. It may be a compound having an anhydride structure. The carbon-carbon double bonds of the polymerizable cyclic acid anhydrides (C) and (G) may be in the ring of the cyclic carboxylic anhydride structure or may be outside the ring.

The polymerizable cyclic acid anhydrides (C) and (G) having carbon-carbon double bonds in the ring of the cyclic carboxylic acid anhydride structure are for example:

[Wherein, R ³¹ and R ³² independently represent a hydrogen atom or a saturated hydrocarbon group having 1 to 10 carbon atoms, and R ³¹ and R ³² become one to form a substituted or unsubstituted ring having 4 to 30 carbon atoms. Can be]

It may be a compound represented by.

Specifically, maleic anhydride (R ³¹ = H, R ³² = H) and citraconic anhydride (R ³¹ = H, R ³² = CH ₃ ) are mentioned.

Polymerizable cyclic acid anhydrides (C) and (G) having a carbon-carbon double bond outside the ring of the cyclic carboxylic acid anhydride structure are, for example:

[Wherein, R ³³ and R ³⁴ become one and have a carbon-carbon double bond and form a substituted (for example, substituted by methyl group or cyclic acid anhydride group) or unsubstituted ring having 4 to 30 carbon atoms. R ³⁵ and R ³⁶ represent a hydrogen atom or a saturated hydrocarbon group (eg an alkyl group) having 1 to 10 carbon atoms. R ³⁷ , R ³⁸ , R ³⁹ , R ⁴⁰ , R ⁴¹ , R ⁴² may independently represent a chlorine atom or a hydrogen atom or a saturated hydrocarbon group having 1 to 10 carbon atoms (such as an alkyl group), and R ³⁷ and R ³⁹ may form a substituted (halogen atom substituted) or an unsubstituted divalent saturated hydrocarbon group having 1 to 10 carbon atoms.

The polymerizable cyclic acid anhydrides (C) and (G) may be as follows, for example.

[Itaconic anhydride]

[Methylated methylcyclohexane tetrabasic anhydride]

[Methyltetrahydrophthalic Anhydride]

[Anhydrous endomethylenetetrahydrophthalic acid]

[Methyl endmethylenetetrahydrophthalic anhydride]

[Anhydrous chloric acid]

The polymerizable cyclic acid anhydrides (C) and (G) preferably have a carbon-carbon double bond and one intramolecular cyclic carboxylic acid anhydride structure, such as maleic anhydride.

The bonding group in the vinyl monomer (D) having a group which bonds with the polymer side chain may be an NCO group, a glycidyl group, an acid chloride group and / or a halomethyl group.

The vinyl monomer (D) having a group bonded to the polymer side chain may be an isocyanate group, a glycidyl group or an acid chloride group-containing vinyl monomer. An isocyanate (NCO) group, glycidyl group or acid chloride group reacts with the active hydrogen group of the polymer side chain to bond the polymer main chain and the polymer side chain.

An isocyanate group containing vinyl monomer means the compound which has a carbon-carbon double bond and an isocyanate group. In general, in an isocyanate group-containing vinyl monomer, the number of carbon-carbon double bonds and isocyanate groups is one. The molecule of the isocyanate group-containing vinyl monomer usually has a carbon-carbon double bond at one end of the molecule and an isocyanate group at the other end.

Examples of isocyanate group-containing vinyl monomers

(i) isocyanate-containing (meth) acrylate esters

(ii) Formula: H ₂ C = C (R ¹¹ ) -A ¹ -NCO

[R ¹¹ is H or a straight, branched or cyclic hydrocarbon group (eg alkyl group) having 1 to 20 carbon atoms (eg 1 to 10), A ¹ is a direct bond or a hydrocarbon group having 1 to 20 carbon atoms]

Vinyl isocyanate, or

(iii) A reaction product of a compound (iii-1) having two isocyanate groups with a compound (iii-2) having a carbon-carbon double bond and active hydrogen.

As isocyanate group containing (meth) acrylate ester (i)

H ₂ C = C (R ¹² ) COO (CH ₂ CH ₂ O) _n (CH ₂ ) _m -NCO

[R ¹² is H or CH ₃ , n is 0 to 20, m is 1 to 20]

(For example, 2-isocyanatoethyl (meth) acrylate) is mentioned.

As vinyl isocyanate (ii)

H ₂ C = C (R ¹³ ) -NCO

[R ¹³ is a straight, branched or cyclic hydrocarbon group having 1 to 20 carbon atoms (such as 1 to 10) (such as an alkyl group or a cyclohexyl group)]

H ₂ C = C (R ¹⁴ )-(CH ₂ ) _n -NCO

[R ¹⁴ is H or a straight, branched or cyclic hydrocarbon group having 1 to 20 carbon atoms (such as 1 to 10) (such as an alkyl group or a cyclohexyl group), n is 2 to 20]

H ₂ C = C (R ¹⁵ ) -Ph-C (R ¹⁶ ) ₂ -NCO

[R ¹⁵ is H or CH ₃ , R ¹⁶ is H or CH ₃ , Ph is a phenylene group].

Examples of the compound (iii-1) having two isocyanate groups include 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, diphenylmethane diisocyanate, naphthalene diisocyanate, hexamethylene diisocyanate, xylene diisocyanate and isophorone di And socyanate.

As the compound (iii-2) having a carbon-carbon double bond and active hydrogen (hereinafter referred to as "monomer having active hydrogen"),

Hydroxyethyl (meth) acrylate,

HO (CH ₂ CH ₂ O) _n COC (R ¹⁷ ) C = CH ₂

[R ¹⁷ is H or CH ₃ , n is 2 to 20],

Amino ethyl (meth) acrylate is mentioned.

The reaction of the compound (iii-1) having two isocyanate groups with the monomer (iii-2) having active hydrogen is carried out in a solvent (especially an aprotic solvent such as an ester solvent), if necessary, dibutyltin dilaurate and the like. It can be carried out using a catalyst of. In the reaction, the amount of the monomer (iii-2) having active hydrogen may be 1.0 to 2.0 equivalents, preferably 1.0 to 1.7 equivalents relative to compound (iii-1) having two isocyanate groups.

As a vinyl monomer which has glycidyl group, glycidyl (meth) acrylate is mentioned.

Examples of the vinyl monomer having an acid chloride include (meth) acryloyl chloride.

When the group which bonds with the polymer side chain is an isocyanate group, a glycidyl group or an acid chloride group, the polymer side chain may be formed of the monomer and the chain transfer agent. The active hydrogen group of the polymer side chain which reacts with the group (ie, isocyanate group, glycidyl group or acid chloride group) which is bonded to the polymer side chain in the polymer main chain is the active hydrogen group of the chain transfer agent bonded to one end of the polymer side chain.

The chain transfer agent may be a chain transfer agent having an active hydrogen group at both ends, such as an alkylene thiol chain transfer agent having an active hydrogen group or an aryl chain transfer agent having an active hydrogen group. Examples of the active hydrogen groups include OH, NH ₂ , SO ₃ H, NHOH, COOH, and SH. Carbon number of the alkylene group of alkylene thiol may be 1-20.

Examples of the alkylene thiol chain transfer agent are as follows.

HS (CH ₂ ) _n OH [n = 2, 4, 6, 11]

HSCH ₂ COOH

HSCH ₂ CH (CH ₃ ) COOH

HSCH ₂ CH ₂ SO ₃ Na

HSCH ₂ CH ₂ SO ₃ H

Examples of aryl chain transfer agents are as follows.

For example, when the group which bonds with the polymer side chain is NCO group, the active hydrogen group of the chain transfer agent reacts with the isocyanate group of the polymer main chain to form -NH-C (= 0) -bond (amide bond). When the active hydrogen group is an OH group, a urethane bond (-NH-C (= O) -O-) is formed. When the active hydrogen group is an NH ₂ group, it forms a urea bond (-NH-C (= 0) -NH-).

The amount of chain transfer agent is no more than 0.7, such as 0.05 to 0.7, in particular 0.1 to 0.5, in molar ratio relative to the amount of branch monomer. A chain transfer agent may be bonded to one end of the polymer side chain obtained by polymerizing the branch monomer. Chain transfer agents can control the length of the chain of the polymer side chain.

The vinyl monomer (D) having a group bonded to the polymer side chain may be a vinyl monomer having a halomethyl group (—CH ₂ X (X: halogen atom)). A polymer main chain and a polymer side chain can couple | bond by replacing the halogen atom in a halomethyl group with a polymer side chain.

The monomer having a halomethyl group may be a monomer having a halomethyl group and a styrene group.

Halomethyl monomers with halomethyl groups have the formula:

[Wherein, R is -CH ₃ or H, R 'is a bond or C _{1 - 3} of alkyl group, X is a halogen atom;

It may be a compound represented by.

Examples of halomethyl monomers are chloromethyl styrene, bromomethyl styrene, 1-chloroethyl styrene and the like. It is preferable that the halogen of a halomethyl group is chlorine.

It is preferable that a polymer main chain and / or a polymer side chain have 2 or more types of repeating units. The polymer backbone and / or polymer side chains may be block polymers or random polymers.

Per 100 parts by weight of the graft copolymer,

The total amount of vinyl monomers (A) and (E) having a perfluoroalkyl group is 10 to 75 parts by weight, such as 10 to 65 parts by weight,

The total amount of the non-fluorine vinyl monomers (B) and (F) is 0 to 89.8 parts by weight, such as 0 to 89, in particular 1 to 50 parts by weight,

The amount of the vinyl monomer (D) having a group bonded to the polymer side chain is 0.1 to 10 parts by weight, such as 1 to 10 parts by weight,

The total amount of the polymerizable cyclic acid anhydrides (C) and (G) is 0.1 to 89.9 parts by weight, such as 0.1 to 50 parts by weight.

The weight ratio of polymer main chain and polymer side chain is 5:95 to 95: 5, preferably 10:90 to 90:10, particularly preferably 30:70 to 70:30.

The polymer backbone is from 0 to 75 parts by weight, such as from 0 to 65 parts, in particular from 1 to 50 parts by weight, of repeating units derived from vinyl monomers (A) having a perfluoroalkyl group relative to 100 parts by weight of the polymer backbone.

The polymer backbone is 0.1 to 89.9 parts by weight, such as 0.1 to 50 parts by weight, of repeating units derived from the polymerizable cyclic acid anhydride (C) with respect to 100 parts by weight of the polymer backbone.

The polymer side chain is 0 to 75 parts by weight, such as 0 to 65, in particular 1 to 50 parts by weight, of repeating units derived from vinyl monomer (E) having a perfluoroalkyl group relative to 100 parts by weight of the polymer side chain.

The polymer side chain is 0 to 75 parts by weight, such as 0 to 50 parts by weight, of repeating units derived from the polymerizable cyclic acid anhydride (G) with respect to 100 parts by weight of the polymer side chain.

The number average molecular weight (GPC in THF, styrene conversion) of the graft copolymer is 5,000 to 200,000, preferably 5,000 to 100,000.

Synthesis of the graft copolymer is performed by graft polymerization by macromonomers, polymer main chains having groups reactive with active hydrogens (NCO groups, glycidyl groups, acid chloride groups), and polymerized by chain transfer agents having active hydrogen groups. A method of reacting a polymer side chain having an active hydrogen group to the polymer, a method of generating living radicals by a halogenated metal catalyst on a polymer main chain having a halomethyl group, such as ATRP (atomic transfer radical polymerization), and replacing a halogen atom with a polymer side chain, The method of polymerizing a branch monomer using a radical, cationic active species, anionic active species, or a chain transfer initiation species such as hydroperoxide (see Japanese Patent Publication No. 61-50082) in the polymer backbone, Macromonomer that makes it easy to control the degree of polymerization of polymer side chains A polymer side chain having an active hydrogen group at one end polymerized by a chain transfer agent having an active hydrogen group is reacted with a polymer main chain having a group (NCO group, glycidyl group, acid chloride group) reactive with graft polymerization or active hydrogen. It is preferable to generate living radicals by a halogenated metal catalyst in the polymer main chain having a halomethyl group, such as the ATRP method, and to replace halogen atoms with polymer side chains.

The preparation of the graft copolymer of the present invention can be performed by any of the following methods (A) or (B), for example, when the group to be bonded to the polymer side chain is an NCO group, a glycidyl group or an acid chloride group.

(A) A method of forming a polymer main chain by copolymerizing a macromonomer obtained by reacting a vinyl monomer having a group with a polymer side chain with a polymer side chain and a copolymerizable monomer (stem monomer) (a stem monomer in the presence of a polymer side chain) Polymerization method), or

(B) A method comprising reacting a branched polymer with a polymer main chain obtained by copolymerizing a monomer capable of copolymerizing with a vinyl monomer having a group bonded to a polymer side chain (method of polymerizing a polymer side chain and a polymer main chain separately).

Method (A) consists of the following processes:

(A-1) polymerizing the monomer (branched monomer) which is a component of a polymer side chain, and the chain transfer agent which exists as needed, and obtaining a polymer side chain;

(A-2) The macromonomer obtained by making the obtained polymer side chain react with the vinyl monomer which has group couple | bonded with a polymer side chain is obtained;

(A-3) A macromonomer is polymerized with a stem monomer to obtain a graft copolymer.

Method (B) consists of the following processes:

(B-1) polymerizing the monomer copolymerizable with the vinyl monomer which has a group which couple | bonds with the polymer side chain which is a component of a polymer main chain, and obtains the polymer main chain which has a group couple | bonded with a polymer side chain;

(B-2) Graft copolymer is obtained by grafting the polymer side chain synthesize | combined separately to the obtained polymer main chain.

The polymerization step (A-1) of the polymer side chain and the polymerization steps (A-3 and B-1) of the polymer main chain can be carried out at a temperature of 70 to 80 ° C. using a polymerization initiator in a solvent. The polymerization time is generally 2 to 12 hours.

The reaction process (A-2 and B-2) of the active hydrogen group of the chain transfer agent which comprises a polymer side chain, and the isocyanate group contained in the monomer which comprises a polymer main chain may be performed at a temperature of 30-65 degreeC in a solvent. The reaction time is generally 2 to 24 hours.

Examples of the polymerization initiator include azobisisobutyronitrile, benzoyl peroxide, di-tert-butyl peroxide, lauryl peroxide, cumene hydroperoxide, tert-butyl peroxide pivalate, diisopropyl peroxydicarbonate, and the like. . The polymerization initiator is preferably in the range of 1 to 10 parts by weight based on 100 parts by weight of the monomer.

The polymerization solvent may be any of a polar solvent, a hydrocarbon solvent, and a mixed solvent thereof. In the case where a group to be bonded to the polymer side chain is present in the reaction system (i.e., steps (A-2), (B-1) and (B-2)), a protic solvent having an active hydrogen group such as an alcohol solvent may be used. Can't.

When the group bonded to the polymer side chain is a halomethyl group, the graft copolymer may be prepared by the following method.

(C-1) A polymer main chain is prepared using a halomethyl monomer (e.g., chloromethylstyrene), another monomer, a solvent, and a polymerization initiator. The solvent is an organic solvent containing no halogen. Examples of the solvent used in the production of the polymer main chain are the same as the examples of the solvent described in the polymer side chain production below. An example of typical polymerization conditions of the polymer backbone is polymerization temperature 110 ° C., time 4 hr. As a polymerization initiator, normal polymerization initiators, such as a peroxide, can be used.

The branch monomer and the halogenated metal catalyst are added to the polymer main chain (C-2) to obtain a graft copolymer in which the polymer side chain is bonded to the polymer main chain.

In the reaction procedure (C-2), the polymer side chain is bonded to the polymer main chain using the reactivity of the halomethyl group (-CH ₂ X (X: halogen atom)) of the polymer main chain. It is believed that a reaction occurs in which living radicals are generated by the metal halide catalyst to replace the halogen atoms in the halomethyl group of the polymer main chain with the polymer side chain. Such a reaction method is called ATRP method (atomic transfer radical polymerization) or ATRA method (atom transfer radical addition) and is described, for example, in JSWang, K.Matyjaszewsky, Macromolecules, 28, 7572 (1955).

The halogen of the metal halide used as the catalyst is preferably chlorine. Examples of metals of halogenated metals are copper (Cu) and Group VIII transition metals (eg iron (Fe), ruthenium (Ru)). Examples of metal halides are CuCl, CuCl ₂ , FeCl ₂ , NiCl ₂ and RuCl ₂ . The amount of the metal halide (such as CuCl) added is 0.1 to 5 mol, preferably 0.5 to 1.5, more preferably 0.8 to 1.2 mol, with respect to 1 mol of halomethyl monomer (such as chloromethylstyrene).

Preference is given to using solubilizers or dispersants (ie accelerators) of metal halides. The accelerator is preferably a compound that coordinates with the halogenated metal to become a ligand and increases the solubility of the halogenated metal in the polymerization solvent. Examples of promoters are organic nitrogen compounds or organic phosphorus compounds. Examples of organic nitrogen compounds (such as amines) are bipyridyl (2,2'-dipyridine), derivatives of 2,2'-dipyridine, such as 4,4'-bis (5-nonyl) -2,2 ' -Dipyridine, triphenylamine, quinoline, tetramethylenediamine, trialkylamine having 2 to 10 carbon atoms of an alkyl group, 1,10-phenanthroline, (CH ₃ ) ₂ N (C ₂ H ₄ N (CH ₃ ) ) _n CH _{3 wherein} n = 1, 2 or 3; Examples of organophosphorus compounds are P (C ₆ H ₅ ) ₃ , P (OC ₆ H ₅ ) ₃ , P (C ₂ H ₅ ) ₃ , P (OC ₂ H ₅ ) ₃ . The amount of promoter is 10 moles or less, such as 0.5 to 8 moles, preferably 1 to 4 moles, and more preferably 1.8 to 3 moles, per mole of metal halide.

The ATRP reaction temperature for forming the polymer side chain is 50 to 250 ° C, preferably 60 to 200 ° C, more preferably 80 to 150 ° C. The reaction temperature is 24 hours or less, for example 1 to 12 hours.

The reaction is preferably carried out in the presence of a solvent. Various non-fluorine solvents may be used as the solvent, but it is preferable to use a hydrocarbon solvent or a polar solvent and a mixed solvent thereof.

Polar solvents are solvents having polar groups in the molecule. Polar groups are hydroxyl groups, carboxyl groups, ester groups, acyl groups, etheroxy groups and the like. Examples of the polar solvent include alcohol solvents, glycol solvents, ester solvents, and ketone solvents.

The hydrocarbon solvent may be a solvent consisting solely of carbon and hydrogen. The hydrocarbon-based solvent may be an aliphatic hydrocarbon. Examples of hydrocarbon solvents are n-heptane, n-hexane, n-octane, cyclohexane, methylcyclohexane, cyclopentane, methylcyclopentane, methylpentane, 2-ethylpentane, isoparaffinic hydrocarbon, liquid paraffin, decane, unde Cannes, Dodecane, Mineral Spirits and Mineral Terpenes. In some cases, an aromatic solvent may be used.

Examples of the alcohol solvent are butyl alcohol, isopropyl alcohol and the like. Examples of the glycol solvent include propylene glycol monomethyl ether, propylene glycol monoethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, and these acetates. Examples of the ester solvent include monobasic esters such as methyl acetate, ethyl acetate and butyl acetate, dibasic succinate, diethyl adipate, dibutyl phthalate, dioctyl phthalate and the like. Examples of ketone solvents are methyl isobutyl ketone (MIBK), methyl ethyl ketone, acetone and the like.

Mixtures of hydrocarbon solvents and polar solvents may be used. The weight ratio of the hydrocarbon solvent and the polar solvent is 100: 0 to 0: 100, such as 5:95 to 95: 5.

The organic solvent solution of the graft copolymer is a solution type water and oil repellent composition.

In the water / oil repellent composition of the present invention, additives such as other water / oil repellent agents, softeners, antistatic agents, crosslinking agents, anti-wrinkle agents and the like can be blended as necessary.

Various things can be mentioned as the to-be-processed object processed by the water / oil repellent composition of this invention. Examples of the workpieces are textiles, glass, paper, wood, leather, fur, asbestos, brick, cement, metals and oxides, ceramic products, plastics, painted surfaces and plasters. Examples of the fiber products include animal and animal natural fibers such as cotton, hemp, wool, and silk, polyamide, polyester, polyvinyl alcohol, polyacrylonitrile, synthetic fibers such as polyvinyl chloride and polypropylene, and semisynthetic such as rayon and acetate. Fibers, or mixed fibers thereof. In order to apply the water / oil repellent composition of the present invention to an untreated object, a method of adhering to the surface of the object to be treated by a known method such as immersion cloth or the like is adopted.

Furthermore, the water / oil repellent composition of the present invention can be used as an aerosol by adding a propellant, for example. Examples of the propellant include fluoroalkane or chlorofluoroalkane having 1 to 2 carbon atoms, LPG gas, dimethyl ether, nitrogen gas or carbon dioxide gas. Representative examples of the fluoroalkane or chlorofluoroalkane having 1 or 2 carbon atoms include dichlorodifluoromethane, trichlorotrifluoromethane, chlorodifluoromethane, chlorodifluoroethane, dichlorotrifluoroethane and tetrafluoro Roethane, a mixture of two or more thereof, and the like. The amount of propellant is preferably 0.05 to 2 times the total weight of the surface treating agent composition including the solvent.

The aerosol is accommodated in a container having a mechanism for injecting the liquid inside the container to the outside, such as an aerosol container, a spray container, or the like.

Preferred Aspects of the Invention

Hereinafter, although an Example is given and this invention is demonstrated concretely, this invention is not limited to these Examples.

The characteristics were measured by the following method.

Water and oil repellency

The polymer solution is diluted with mineral spirits so that the solids concentration is 0.8% by weight and applied to the cloth so that it is moistened with hand spray. As cloth, polyester cloth, polyester / cotton blend cloth, and cotton cloth are used. After drying for 10 hours at room temperature, water repellency and oil repellency are evaluated in the following manner.

Water repellency is a water repellent No. by the spray method of JIS-L-1092 (1998). (See Table 1 below).

The oil repellency was measured by AATCC-TM118 by dropping a few drops of the test solution shown in Table 2 into two places on the test cloth to observe the penetration state after 30 seconds. It is oil-repellent.

Water repellency No. condition 5 Without adhesion to surface wet 4 Showing some adhesion wetting on the surface 3 With partial wetting on the surface 2 Showing wetting on the surface One Showing wetting throughout the surface

Oil repellent Test solution Surface tension (dyne / cm, 25 ℃) 8 n-heptane 20.0 7 n-octane 21.8 6 n-decane 23.5 5 n-dodecane 25.0 4 n-tetradecane 26.7 3 n-hexadecane 27.3 2 n-hexadecane 35 / Nusol 65 solution 29.6 One Nusol 31.2 0 Less than 1 -

Product stability

The polymer solution is adjusted to a concentration of 15% by weight with a petroleum solvent, and then stored at −5 ° C. for 1 month to evaluate whether solidification or precipitation occurs. The aromatic-containing solvent is dissolved in mineral spirit, and the non-aromatic solvent is n. Dissolve in decane and evaluate.

○: maintain a uniform liquid

×: solidification or precipitation

Dilution Stability

The polymer solution is diluted with n-decane to a concentration of 0.8% by weight of solids, stored at −5 ° C. for 1 month, and evaluated for solidification or precipitation.

○: uniform liquid and transparent

△: opaque but uniform and usable level

×: solidification or precipitation

Synthesis Example  1 (containing isocyanate Vinyl monomer  synthesis)

In a 500 ml three-necked flask equipped with a dropping funnel

100 g of 2,4-tolylene diisocyanate

100 g of ethyl acetate

0.1 g of dibutyltin dilaurate

Injecting, shaking at 60-65 ℃,

90 g of hydroxyethyl methacrylate

90 g of ethyl acetate

Is added dropwise over 15 minutes through a dropping funnel and reacted for 8 hours to obtain an isocyanate group-containing vinyl monomer (a) shown below:

Example  One

The following were put into a 1000 ml glass-made polymerization sample, and it reacted at 75 degreeC for 8 hours, shaking, under nitrogen atmosphere, and a polymer side chain is obtained.

3 g of metcaptoethanol

CF ₃ CF ₂ (C ₂ F ₂ ) _n C ₂ H ₂ OCOCH = CH ₂ (average n = 3.5) (FA) 95 g

Stearyl methacrylate (StMA) 5 g

0.17 g of azoisobutyronitrile

120 g of ethyl acetate

After the reaction, the monomer consumption rate by gas chromatography was 100%. According to NMR, the composition ratio (molar ratio) of each component in a polymer was mercaptoethanol: FA: StMA = 1.0: 4.8: 0.8.

Subsequently, the temperature is lowered from 55 ° C. to 60 ° C., 9 g of 2-isocyanate ethyl methacrylate is added in an air atmosphere, and reacted at 55 ° C. to 60 ° C. for 8 hours while shaking to obtain a macromonomer. After the reaction, the absorption peak of the NCO group in the IR spectrum was almost lost.

Subsequently, the following are added to a macromonomer, and it reacts at 75 degreeC for 8 hours, shaking in nitrogen atmosphere, and obtains a graft copolymer.

100 g of 2-ethylhexyl methacrylate (2-EHMA)

Maleic anhydride (MAN) 10 g

515 g of ethyl acetate

9 g tert-butylperoxy pivalate

(Made by Nippon Yushi, perbutyl PV)

After the reaction, the monomer consumption rate by gas chromatography was 100%. According to GPC, the number average molecular weight of the obtained polymer was 8,000.

The water and oil repellency, product stability, and dilution stability of the obtained polymer solution were measured. The results are shown in Table 10.

Example  2

Synthesis was carried out in the same manner as in Example 1, except that 38 g of a solution (50% by weight) of the isocyanate group-containing vinyl monomer (a) prepared in Synthesis Example 1 was used instead of 2-isocyanate ethyl methacrylate.

In each preparation of the polymer side chain and the graft copolymer, the monomer consumption was 100%. According to NMR, the composition ratio (molar ratio) of each component in the polymer side chain was mercaptoethanol: FA: StMA = 1.0: 4.7: 0.6.

In addition, the NCO absorption of the IR spectrum during macromerization was almost lost. According to GPC, the number average molecular weight of the obtained graft polymer was 8,000.

The water and oil repellency, product stability, and dilution stability of the obtained polymer solution were measured. The results are shown in Table 10.

Example  3 to 6

The procedure of Example 1 was repeated except using the monomer shown in Table 3.

In each preparation of the polymer side chain and the graft copolymer, the monomer consumption was 100%. According to NMR, the composition ratio (molar ratio) of each component in the polymer was mercaptoethanol: FA: 2-EHMA = 1.0: 5.2: 1.8 in Example 4, and mercaptoethanol: FA: MAN = 1.0: 5.0: 1.2 in Example 5. In Example 6, mercaptoethanol: FA: StMA = 1.0: 5.8: 1.9.

In addition, NCO absorption in the IR spectrum of the macromerization reaction was almost lost.

According to GPC, the number average molecular weight of the obtained graft polymer was 9,300 in Example 3, 8,900 in Example 4, 8,600 in Example 5, and 8,200 in Example 6.

The water and oil repellency, product stability, and dilution stability of the obtained polymer solution were measured. The results are shown in Table 10.

Ingredients (g) Polymer side chains Polymer backbone Macromonomer Mercaptoethanol FA Stma 2-EHMA MAN 2-isocyanatoethyl methacrylate Isocyanate group-containing vinyl monomers (a) FA 2-EHMA MAN Example 1 3 95 5 - - 9 - - 100 10 Example 2 3 95 5 - - - 38 - 100 10 Example 3 3 95 5 - - 9 - - 106 4 Example 4 3 95 - 5 9 - - 100 10 Example 5 3 95 - - 5 9 - - 105 5 Example 6 3 90 10 - - 9 - 5 95 10

Example  7

The following was put into a 1000 ml glass-made polymerization sample, and it reacted at 75 degreeC for 8 hours, shaking, under nitrogen atmosphere, ethyl acetate was distilled off and a polymer side chain was obtained.

3 g of mercaptoacetic acid

FA 95 g

Stearyl methacrylate (StMA) 5 g

0.09 g of azoisobutyronitrile

120 g of ethyl acetate

In the preparation of the polymer side chain, the monomer consumption rate by gas chromatography was 100%. According to NMR, the composition ratio (molar ratio) of each component in a polymer was mercaptoethanol: FA: StMA = 1.0: 6.1: 1.3.

Subsequently, 5 g of glycidyl methacrylate (GMA) and 1 g of N, N-dimethyllaurylamine were added to the polymer side chain solution to which 150 g of methyl isobutyl ketone was added, and the mixture was shaken for 10 hours while shaking. To obtain a macromonomer. After the reaction, the consumption rate of glycidyl methacrylate by gas chromatography was 100%.

Subsequently, the following are added to a macromonomer, and it reacts at 75 degreeC for 8 hours, shaking in nitrogen atmosphere, and obtains a graft copolymer.

100 g of 2-ethylhexyl methacrylate (2-EHMA)

Maleic anhydride (MAN) 10 g

465 g of methyl isobutyl ketone

9 g tert-butylperoxy pivalate

(Made by Nippon Yushi, perbutyl PV)

After the reaction, the monomer consumption rate by gas chromatography was 100%. According to GPC, the number average molecular weight of the obtained polymer was 9,400.

The water and oil repellency, product stability, and dilution stability of the obtained polymer solution were measured. The results are shown in Table 10.

Example  8 to 10

The same procedure as in Example 7 was repeated to polymerize the monomer shown in Table 4.

In each preparation of the polymer side chain and the graft copolymer, the monomer consumption was 100%. According to NMR, the composition ratio (molar ratio) of each component in the polymer was mercaptoacetic acid: FA: 2-EHMA = 1.0: 6.5: 2.1 in Example 8, and mercaptoacetic acid: FA: MAN = 1.0: 6.9: 1.6 in Example 9. In Example 10, mercaptoacetic acid: FA: StMA = 1.0: 7.1: 2.2.

In addition, the consumption rate of glycidyl methacrylate by gas chromatography after reaction was 100%.

According to GPC, the number average molecular weight of the obtained graft polymer was 9,300 in Example 8, 8,900 in Example 9, and 8,600 in Example 10.

The water and oil repellency, product stability, and dilution stability of the obtained polymer solution were measured. The results are shown in Table 10.

Ingredients (g) Polymer side chains Polymer backbone Macromonomer Mercaptoacetic acid FA Stma 2-EHMA MAN GMA FA 2-EHMA MAN Example 7 3 95 5 - - 5 - 100 10 Example 8 3 95 - 5 - 5 - 100 10 Example 9 3 95 - - 5 5 - 106 4 Example 10 3 90 10 - - 5 5 95 10

Example  11

(Step 1 Polymer Main Chain Polymerization)

The following are put into a 500 mL glass-made polymerization sample, and the polymer main chain which made it react for 8 hours at 80 degreeC, shaking in nitrogen atmosphere is obtained.

5 g of chloromethylstyrene (CMS)

90 g of 2-ethylhexyl methacrylate (2-EHMA)

Maleic anhydride (MAN) 9 g

100 g of diethyl succinate

4 g tert-butylperoxy pivalate

(Made by Nippon Yushi, perbutyl PV)

After the reaction, the monomer consumption rate by gas chromatography was 100%.

(Stage 2 polymer side chain polymerization)

Next, the following were added to the polymer backbone solution.

FA 100 g

10 g of 2-ethylhexyl methacrylate (2-EHMA)

Cuprous chloride 3 g

10 g of bipyridyl

100 g of mineral terpene

Furthermore, it is made to react at 110 degreeC for 8 hours, shaking in nitrogen atmosphere, and the graft copolymer which the polymer side chain couple | bonded with the polymer main chain is obtained. After the reaction, the monomer loss rate by gas chromatography was 100%.

Subsequently, it adjusted so that it might become 15 weight% of solid content with mineral terpene, and activated carbon was thrown in the ratio of 10 weight% with respect to the solution. After shaking for 2 hours at room temperature, the activated carbon was filtered off with a filter paper.

The obtained filtrate was confirmed by plasma luminescence analysis (ICP) that copper did not remain. According to GPC, the number average molecular weight of the obtained graft polymer was 11,200.

The water and oil repellency, product stability, and dilution stability of the obtained polymer solution were measured. The results are shown in Table 10.

Example  12 and 13

The same procedure as in Example 11 was repeated to polymerize the monomer shown in Table 5.

The monomer consumption by gas chromatography after the reaction in each of the polymer main chain and polymer side chains was 100%.

According to GPC, the number average molecular weight of the obtained graft polymer was 9,600 in Example 12 and 10,900 in Example 13.

Ingredients (g) First stage polymerization (polymer backbone) Second stage polymerization (polymer side chain) CMS 2-EHMA FA MAN FA 2-EHMA MAN Example 11 5 90 - 9 100 10 - Example 12 5 95 - 4 100 5 5 Example 13 5 85 5 9 100 10 -

Comparative example  1 to 4

The same procedure as in Example 1 and Example 2 was repeated, and the monomer shown in Table 6 was polymerized.

In each preparation of the polymer side chain and the graft copolymer, the monomer consumption was 100%. According to NMR, the composition ratio (molar ratio) of each component in a polymer side chain was mercaptoethanol: FA: StMA = 1.0: 4.7: 0.9 in the comparative example 1, and mercaptoethanol: FA: StMA = 1.0: 4.8: 0.6 in the comparative example 2 In Comparative Example 3, mercaptoethanol: FA: 2-EHMA = 1.0: 5.1: 1.5, and in Comparative Example 4, mercaptoethanol: FA: StMA = 1.0: 4.8: 0.7.

In addition, the NCO absorption of the IR spectrum during macromerization was almost lost. According to GPC, the number average molecular weight of the obtained graft polymer was 8,600 in the comparative example 1, 8,500 in the comparative example 2, 8,000 in the comparative example 3, and 9,400 in the comparative example 4.

The water and oil repellency, product stability, and dilution stability of the obtained polymer solution were measured. The results are shown in Table 11.

Ingredients (g) Polymer side chains Polymer backbone Macromonomer Mercapto ethanol FA Stma 2-EHMA 2-isocyanatoethyl methacrylate Isocyanate group-containing vinyl monomers (a) 2-EHMA HEMA Comparative Example 1 3 95 5 - 9 - 110 - Comparative Example 2 3 95 5 - - 38 110 - Comparative Example 3 3 95 - 5 9 - 110 - Comparative Example 4 3 95 5 - 9 - 100 10

Note) HEMA: hydroxyethyl methacrylate

Comparative example  5 to 7

The same procedure as in Example 7 was repeated to polymerize the monomer shown in Table 7.

In each preparation of the polymer side chain and the graft copolymer, the monomer consumption was 100%. According to NMR, the composition ratio (molar ratio) of each component in the polymer side chain was mercaptoacetic acid: FA: StMA = 1.0: 6.0: 1.3 in Comparative Example 5, and mercaptoacetic acid: FA: 2-EHMA = 1.0: 6.4 in Comparative Example 6 : 2.2, and in Comparative Example 7, mercaptoacetic acid: FA: StMA = 1.0: 6.9: 1.5.

In addition, the reaction rate of glycidyl methacrylate by gas chromatography at the end of macromerization reaction was 100%. According to GPC, the number average molecular weight of the obtained graft polymer was 9,100 in the comparative example 5, 8,600 in the comparative example 6, and 8,900 in the comparative example 7.

The water and oil repellency, product stability, and dilution stability of the obtained polymer solution were measured. The results are shown in Table 11.

Ingredients (g) Polymer side chains Polymer backbone Macromonomer Mercaptoacetic acid FA Stma 2-EHMA GMA 2-EHMA HEMA Comparative Example 5 3 95 5 - 5 110 - Comparative Example 6 3 95 5 5 110 - Comparative Example 7 3 95 5 - 5 100 10

Comparative example  8 and 9

The same procedure as in Example 11 was repeated to polymerize the monomer shown in Table 8. The monomer consumption by gas chromatography after the reaction in each of the polymer main chain and polymer side chains was 100%.

According to GPC, the number average molecular weight of the obtained graft polymer was 11,600 in Example 12 and 12,300 in Example 13.

The water and oil repellency, product stability, and dilution stability of the obtained polymer solution were measured. The results are shown in Table 11.

Ingredients (g) First stage polymerization (polymer backbone) 2nd stage polymerization (polymer side chain) CMS 2-EHMA HEMA FA 2-EHMA Comparative Example 8 5 99 - 100 10 Comparative Example 9 5 90 9 100 10

Comparative example  10

To 1.0 equivalent of 2-isocyanatoethyl methacrylate is reacted at 50 ° C for 12 hours in ethyl acetate in the presence of 0.7 equivalent of mercaptoethanol and 0.1% by weight of dibutyltin dilaurate.

Subsequently, 5.5 g of the reactant (reactant of an isocyanate group-containing vinyl monomer and mercaptoethanol) and the following are added to a 1000 ml glass polymerized sample, and reacted at 75 ° C. for 8 hours while shaking under a nitrogen atmosphere to obtain a polymer.

FA 42.7 g

Stearyl methacrylate (StMA) 2.3 g

45.0 g of 2-ethylhexyl methacrylate (2-EHMA)

Maleic anhydride (MAN) 4.5 g

515 g of ethyl acetate

9 g tert-butylperoxy pivalate

According to GPC, the number average molecular weight of the obtained random polymer was 15,000. The water and oil repellency, product stability, and dilution stability of the obtained polymer solution were measured. The results are shown in Table 11.

Comparative example  11

The monomer shown in Table 9 was polymerized in the same procedure as in Example 10.

According to GPC, the number average molecular weight of the obtained random polymer was 13,400. The water and oil repellency, product stability, and dilution stability of the obtained polymer solution were measured. The results are shown in Table 11.

Comparative example  12

To 1.0 equivalent of 2-glycidyl methacrylate, the reaction was carried out at 50 ° C for 12 hours in ethyl acetate in the presence of 0.7 equivalent of 1.0 wt% of mercaptoethanol N, N-dimethyllaurylamine.

Subsequently, 3.7 g of the reactant (reactant of glycidyl methacrylate and mercaptoacetic acid) obtained in the 1000 mL glass polymerized sample and the following are added, followed by reaction at 75 ° C. for 8 hours with shaking under a nitrogen atmosphere to obtain a polymer.

FA 43.5 g

Stearyl methacrylate (StMA) 2.3 g

46.0 g of 2-ethylhexyl methacrylate (2-EHMA)

Maleic anhydride (MAN) 4.6 g

515 g of ethyl acetate

9 g tert-butylperoxy pivalate

According to GPC, the number average molecular weight of the obtained random polymer was 14,500. The water and oil repellency, product stability, and dilution stability of the obtained polymer solution were measured. The results are shown in Table 11.

Comparative example  13

The following was added to a 1000 ml glass-made polymerization sample, and it reacted at 75 degreeC for 8 hours, shaking in nitrogen atmosphere, and a polymer is obtained.

FA 46.7 g

2-ethylhexyl methacrylate (2-EHMA) 46.7 g

Maleic anhydride (MAN) 4.3 g

Chloromethylstyrene (CMS) 2.3 g

515 g of ethyl acetate

9 g tert-butylperoxy pivalate

According to GPC, the number average molecular weight of the obtained random polymer was 13,600. The water and oil repellency, product stability, and dilution stability of the obtained polymer solution were measured. The results are shown in Table 11.

Ingredients (g) FA Stma 2-EHMA MAN 2-isocyanatoethyl methacrylate and mercaptoethanol reacted Compounds reacted with GMA and mercaptoacetic acid CMS Comparative Example 10 42.7 2.3 45.0 4.5 5.5 - - Comparative Example 11 42.7 - 47.3 4.5 5.5 - - Comparative Example 12 43.5 2.3 46.0 4.6 - 3.7 - Comparative Example 13 46.7 - 46.7 4.3 - - 2.3

Water repellency Oil repellent Product stability Dilution Stability Polyester if Polyester if In aromatic-containing solvents In non-aromatic solvent Example 1 5 5 5 6 ○ ○ ○ Example 2 5 5 5 6 ○ ○ ○ Example 3 5 5 4 6 ○ ○ ○ Example 4 5 5 4 6 ○ ○ ○ Example 5 5 5 5 6 ○ ○ ○ Example 6 5 5 4 6 ○ ○ ○ Example 7 5 5 5 6 ○ ○ ○ Example 8 4 5 4 6 ○ ○ ○ Example 9 5 5 5 6 ○ ○ ○ Example 10 5 5 4 6 ○ ○ ○ Example 11 5 5 8 8 ○ ○ ○ Example 12 5 5 7 7 ○ ○ ○ Example 13 4 5 8 7 ○ ○ ○

Water repellency Oil repellent Product stability Dilution Stability Polyester if Polyester if In aromatic-containing solvents In non-aromatic solvent Comparative Example 1 5 3 2 2 △ × × Comparative Example 2 5 3 2 3 △ △ ○ Comparative Example 3 4 3 2 2 △ × × Comparative Example 4 3 3 3 3 × × × Comparative Example 5 2 2 0 0 △ × × Comparative Example 6 2 2 0 0 △ × × Comparative Example 7 3 2 0 0 △ × × Comparative Example 8 5 3 4 3 ○ △ △ Comparative Example 9 5 3 4 4 ○ × × Comparative Example 10 2 One One One × × × Comparative Example 11 2 One 2 One × × × Comparative Example 12 One One 2 One × × × Comparative Example 13 One One 2 One × × ×

By introducing the cyclic acid anhydride into the molecule of the graft copolymer, the solubility in the petroleum solvent is improved, and the water repellency is improved by improving the adhesion to the fiber due to the polarity of the anhydrous structure.

Claims (4)

As a graft copolymer having a repeating unit derived from a vinyl monomer having a perfluoroalkyl group and a repeating unit derived from a polymerizable cyclic acid anhydride, In graft copolymers, Polymer backbone      (A) a vinyl monomer having a perfluoroalkyl group,      (B) non-fluorine vinyl monomers, and      (C) polymerizable cyclic acid anhydride       Consists of one or more monomers selected from the group consisting of      (D) also comprises a vinyl monomer having a group bonded to the polymer side chain, Polymer side chains      (E) a vinyl monomer containing a perfluoroalkyl group,      (F) non-fluorine vinyl monomers, and      (G) polymerizable cyclic acid anhydride      Consists of one or more monomers selected from the group consisting of At least one of the said component (A) and a component (E) is an essential component, at least one of the said component (C) and a component (G) is an essential component, The graft copolymer in which the binding group in the vinyl monomer (D) having a group which binds to the polymer side chain is at least one group selected from the group consisting of NCO group, glycidyl group, acid chloride group and halomethyl group. The method of claim 1, based on 100 parts by weight of the graft copolymer, The total amount of component (A) and (E) is 10-75 weight part, The total amount of component (B) and (F) is 0-89.8 weight part, The amount of component (D) is 0.1 to 10 parts by weight, The graft copolymer whose total amount of component (C) and (G) is 0.1-89.9 weight part. The graft copolymer of claim 1, wherein the polymerizable cyclic acid anhydride has a carbon-carbon double bond copolymerizable with a vinyl monomer in one molecule, and at least one intramolecular cyclic carboxylic acid anhydride structure. The method of claim 1, (I) Polymeric cyclic acid anhydride (C), containing a polymer backbone that does not contain a vinyl monomer (A) having a perfluoroalkyl group, a perfluoroalkyl group-containing vinyl monomer (E), and a polymerizable cyclic Graft copolymers having a polymer side chain containing no acid anhydride (G); And (II) a polymer main chain containing a polymerizable cyclic acid anhydride (C) and not containing a vinyl monomer (A) having a perfluoroalkyl group, a perfluoroalkyl group-containing vinyl monomer (E) and a polymerizable cyclic acid anhydride ( Graft copolymers with polymer side chains containing G) Graft copolymer which is at least one polymer selected from the group consisting of.